Process for producing cyclododecatrienes

ABSTRACT

Crude butadiene-1,3 which is a B-B fraction is subjected to catalytic trimerization to produce cyclododecatriene-1,5,9 in the presence of a Ziegler-type catalyst comprising a Ti-compound, e.g., Ti (OPrCl)Cl3, an Al-compound, e.g., AlEt2Cl, and electrondonor compounds containing S and containing P, e.g., dimethyl sulfoxide and triphenyl phosphate.

waited States Patent 1 Morikawa et al.

1 Sept. 11, 1973 PROCESS FOR PRODUCING CYCLODODECATRIENES lnventors:Hiroyuki Morikawa; Akiya Nakamura; Noriyoshi Tamura;

Kazuo Yamagishi, all of Ami-machi,

Japan Mitsubishi Petrochemical Company, Limited, Tokyo-to, Japan Filed:Dec. 14, 1971 Appl. No.: 207,955

Assignee:

Foreign Application Priority Data Dec 25, 1970 Japan 45/117720 US. Cl.260/666 B, 252/431 P Int. Cl. C07c 3/00 Field of Search 260/666 B;

References Cited UNITED STATES PATENTS 2/1972 Furukawa et a1. 260/666 Bcatalyst 3,644,548 2/1972 Takahasi et al. 260/666 B 3,663,639 5/1972Morikawa et al. 260/666 B 3,076,045 1/1963 Schneider et al. 260/666 B3,149,173 9/1964 Wittenberg et al. 260/666 B 3,636,174 1/1972 Nakamuraet al 260/666 B Primary Examiner-Delbert E. Gantz AssistantExaminer-Veronica O'Keefe A ttorney- E. F. Wenderoth, Michael R. Daviset a1.

[57] ABSTRACT 7 Claims, No Drawings PROCESS FOR PRODUCINGCYCLODODECATRIENES' BACKGROUND OF THE INVENTION This invention relatesto a process for producing cyclododecatrienes of high purity frombutadiene of low purity.

It is well known that the cyclic trimer of butadiene can be produced bysubjecting it to catalytic trimerization, and that Ziegler catalysts(consisting of, in combination, a transition metal component and anorganometallic compound, and sometimes including denatur- I ants ormodifiers such as electron-donor compounds) constitute a group of thecatalysts that can be used for the trimerization. Titanium compounds andorganoaluminum compounds are a representative transition metal componentand an organometalic compound, respectively, and electron donativecompounds containing nitrogen, oxygen, phosphorus, or sulphur are wellsuited for the denaturant.

When high purity butadiene is used as a starting material, there arevarious known processes for cyclic trimerization over through the use ofsuch a Ziegler type catalyst. If high purity cyclododecatriene could be-DETAILED DESCRlPTlON As has been mentioned above, the use of a specificZiegler-type catalyst, which is an important requisite for thisinvention, resulted from the development of our preceding invention(Japanese Pat. No. 45-52395 (1970). In this preceding invention, wefound that catalysts of Ti(ORCl),,Cl ,,-AlR,,, Cl -80R", and/or POR',series make it possible to produce high purity cyclododecatrienes fromlow purity butadiene admixed with acetylenic hydrocarbons and allene.

Further investigations on the denaturated catalyst brought us to thediscovery that when the cyclopentadiene included in a BB fraction wasremoved, not only was the yield of the obtained cyclododecatrieneimproved remarkably, but the purity of the cyclododecatrienes producedwas far higher. Moreover, it was a great surprise to discover that evenwhen acetylene and allene existed in the fraction up to an amount ofabout 30,000 ppm, high purity cyclododecatrienes could be obtained byusing this denaturated catalyst, but when cyclopentadiene was present inan amount of more than 1,000 ppm, it become difficult to obtaincyclododecatrienes of high purity.

Therefore, on the basis of this invention developed from the precedinginvention, the yield and purity of the cyclododecatrienes which areobtained from a BB fraction without removing acetylenic hydrocarbons andallene by prehydrogenation are remarkably high when the BB fraction isfreed from cyclopentadiene or it contains a smaller amount ofcyclopentadiene, because the catalyst is resistant to acetylenic hy- Asto the impurity poisoning the catalyst that is used for thetrimerization of butadiene, acetylene and allene are known (Annalen No.681, p. 10, (1965)). Consequently, even when high purity butadiene isused as a starting material, a prehydrogenation process is usuallyrequired for removingthese impurities.

Therefore, a BB fraction containing large amounts of acetylenichydrocarbons and allene and other impurities can not be used as astarting materialfor the production of high purity cyclododecatrienesuntil ithas drocarbons and allene.

The present invention has an important significance in establishingstandardsfor judging the quality of a BB fraction which will be used asa butadienecontaining starting material for the production ofcyclododecatrienes, and, further, on the point of practical performancewherein the process of removing cyclopentadiene is usually simpler thanthat 'of prehydrogenation, and the only measure for the decrease of thecyclopentadiene content being to slightly modify been purified to aconsiderably high degree-of purity beforehand.

SUMMARY OF THE INVENTION An object of thisinventionis to provide anindustrial possibility of producing cyclododecatrienes through the useof a BB fraction asa starting material. We have found that this objectcan be achieved by controlling the impurities of the BB fraction andusing a special Ziegler-type catalyst.

Consequently, the process for producing cyclododecatriene-( 1,5,9)according to this invention is characterizedin that a BB fraction(containing 25 90 percent by weight of butadiene), of which thecyclopentadiene content is controlled to less than 0.1 weight per cent,is brought into-contact with a Ziegler-type.

catalyst comprising a titanium compound, an aluminum compound, anelectron-donor compound containing phosphorus andan electron-donorcompound containing sulphur, its butadiene thus undergoing cyclictrimerization. I

the proceduresfor recovering the BB fraction in the naphthadecomposition process. v

The catalyst used'in the present invention comprises,

in combination, a titanium compound, an organoaluminum compound, andorganic compounds containing phosphorus andsulphur:

Titanium compound r Titanium compounds representable by the generalformula TiX,-,Y,-, (wherein X is a halogen, Y is an alkoxy group, acycloalkoxy group, a chloroalkoxy group (each of alkoxy moietiesthere-of having from one to alkoxy'group, a cycloalkoxygroup (eachhaving from one to about 10 carbon atoms), an aryloxy group (a phenoxygroup or a methylphenoxy group), an acetylacetonato group) are suitable.

EXAMPLES: Titanium tetrachloride Titanium tetrabromide "Titaniumbutoxytrichloride EXAMPLES:

Dimethylaluminum chloride Diethylaluminum chloride Diisobutylaluminurnchloride Diphenylaluminum chloride Dioctylaluminum chlorideMethylaluminum sesquichloride Ethylaluminum sesquichloride Butylaluminumsesquichloride Electron-donor compounds A. Phosphorus compoundsrepresentable by the general formula PRO", wherein R" is an alkyl group,a cycloalkyl group (each having from one to about 10 carbons), an arylgroup (a phenyl group or a methylsubstituted phenyl group), an alkoxygroup (of from one to about l carbons) and an aryloxy group in which thearyl moiety is phenyl or a methyl-substituted phenyl group are suitable.

EXAMPLE:

Trimethylphosphine oxide Triethylphosphine oxide Tripropylphosphineoxide Tributylphosphineoxide Triphenylphosphine oxide Tricresylphosphineoxide Trimethyl phosphate Triethyl phosphate Tributyl phosphateTriphenyl phosphate Tricresyl phosphate B. Sulphur compoundsrepresentable by the general formula SOR', (wherein R' is an alkyl group(of from one to about carbons), an aryl group (a phenyl group, or amethyl-substituted group) are suitable.

EXAMPLE:

Dimethyl sulfoxide Dipropyl sulfoxide Dibutyl sulfoxide Diphenylsulfoxide Catalyst composition The ratio of the titanium compoundcontent to the aluminum compound content of the catalyst system to beused can be varied over a wide range. In general, Al/Ti as a molar ratiois from one to l00, preferably from 3 to l0.

The electron-donor compound content of the catalyst system, ascalculated with respect to a phosphorus compound (P) and a sulphurcompound (S), is P+S/Ti 0.10 to 4.0 as a molar ratio, preferably 0.1 to1.0, and P/S 0.01 to 10.0, preferably 0.1 to 3.0.

Method of preparing the catalyst The catalyst can be readily prepared bymixing the compounds in a stream of an inert gas or in a vapour streamof the starting material BB fraction. It is desirable that the titaniumcompound, electron-donor compound, and aluminum compound be added inthis order.

Trimerization reaction: Solvent The trimerization can be carried outeither in the presence of or in the absence of a solvent, but usuallyits operation is preferably peformed in the presence of a solvent.

As for the solvent to be used, a solvent which can be used in such acatalytic trimerization reaction, for example, an aromatic hydrocarbonsuch as benzene, toluene, xylene, etc., or an aliphatic hydrocarbon suchas hexane, heptane, is suitable.

Reaction temperature and pressure The reaction temperature can be variedin a range of from 0 to 100C, preferably in a range of from 30 to C. Thereaction can be carried out either at atmospheric pressure or under ahigher pressure.

Starting material: BB fraction The term BB fraction as used hereindesignates a C -fracti0n obtained in the naphtha decomposition. (Thenaphtha decomposition is a process for producing unsaturated olefins ordienes usually from naphtha by subjecting it to thermal decomposition.For details of the process, Petroleum and Petroleum Chemistry Vol.12,No.1, p. 47 should be referred to.

The fraction is a mixture having usually the following composition(weight 1,3-Butadiene 25 50 percent Butene Butane 50 70 percent Allene0.02 2 percent Methylacetylene 0.02 2 percent Ethylacetylene 0.05 2percent Vinylacetylene 0.05 2 percent Cyclopentadiene 0.1 2 percent TheBB fraction to be obtained from'the naphtha decomposition process isusually isolated by. distillation, so that it .canbe considered that apurification processhas taken place to some degree. Nevertheless, whenit is used as a starting material of this invention, furtherdistillation may be carried out as needed. Consequently, the BB fractiondefined in this invention is one containing from 25 to percent ofbutadiene. Butadiene content and other features The butadiene content isfrom 25 to 90 percent by weight, and the effectiveness of this inventionis fully exhibited provided that the butadiene content is in this range.

Further, as a result of our investigations, we found that when thebutadiene content is increased to from 60 to 90 percent by weight, thepurity of the resulting cyclododecatriene is always from 99.8 to 99.98percent, which has the advantage of remarkably simplifying thepurification process.

Therefore, it is certainly preferable that the butadiene content beconcentrated up to from 60 to 90 percent by weight along withcontrolling the cyclopentadiene content to less than 0.1 weight percent.

It is desirable that the acetylene and allene contents be less than 3percent by weight.

EXAMPLES:

Example for comparison In Table 1, the results of a study in connectionwith various titanium-containing catalysts are shown. It is apparentthat the cyclopentadiene content of a crude BB fraction has a greateffect on the yield and purity of the cyclododecatriene produced.Consequently, cyclododecatrienes of an industrially sufficient highpurity can be obtained by controlling the cyclopentadiene content of thecrude BB fraction to less than 0.1 weight percent in a pretreatmentprocess.

The use of a crude BB fraction containing more than 0.10 percentcyclopentadiene, without carrying out the process of this invention,results in a considerable decreases of the yield of the producedcyclododecatriene and, in addition, a lowering of the purity thereof.

TABLE 1 effect of the cyclopentadiene content of a starting material BBfraction Titanium Cyclopen- Yield of Purity of compound tadienecyclodode cyclododein content in catriene catriene catalyst BBfracfraction tion (weight '%2) (weight (weight Ti(0PrCl)Cl, 0.15 2683.09

Ti(OBu)Cl, 0.15 18 i 81.10

Ti(OBu) 0.15 3 80.5

Note 1: The yield of cyclododecatriene is the weight percentage of theproduced pure cyclododecatriene based on the amount of butadienesupplied.

Note 2: The purity of cyclododecatriene fraction is determined byanalyzing the cyclododecatriene traction at 235 250C at the productusing a gas chromatograph equipped with a capillary column (Apiezon- L,40m, 148C) I Note 3: The gas composition of the starting material BBfraction (weight 96) V 1,3-Butadiene 37.0; Allene 0.20; Methylacetylene0.10; Ethylacetylene 0.10; Vinylacetylene 0.40; Cyclopentadiene (Tablel).

The remainder is a mixture of butane, butenel, butene-Z and isobutene.

Note 4: Reaction conditions Benzene l00c.c.; titanium compound 1 m.mol.;diethyl-aluminum chloride 0.606 g.; Triphenyl phosphate 0.026g.;dimethyl sulfoxide 0.064g.; reaction temperature 75C; reaction time 3hours. 7

EXAMPLE -1 The atmosphere of an autoclave of a volume of 500 c.c. wasreplaced with argon gas, then l00c.c. of benzene, 0.258g. ofchloropropoxytrichlorotitanium', 0.606g. of diethylaluminum chloride,0.026g. of triphenyl phosphate, and 0.064g. of dimethyl sulfoxide wereadded and mixed at 40C to prepare a catalyst.

Next, the autoclave was charged with 62g of a 13-43 EXAMPLE 2 By using62g. of a BB fraction containing 0 percent cyclopentadiene (the otherconstituents were the same as in Example 1) as a raw material and thesame treatment as in Example 1 was carried out.

A cyclododecatriene fraction was obtained in an amount of 17.6 g. (99.89percent pure) in a yield of 76.6 per cent.

EXAMPLE 3 By using l00c.c. of benzene, 0.278 g. of di(chloroethoxy)-dichlorotitanium, 0.606g. of diethylaluminum chloride, 0.020g. oftributylphosphine oxide, 0.064g. of dimethyl sulfoxide, and 62g. of a BBfraction (having the same composition as in Example 1 except thecyclopentadiene content was 0.10 percent), the same treatment as inExample 1 was carried out.

A cyclododecatriene fraction was obtained in an amount of 14.6 g. (98.9percent pure), and its yield was 63 per cent. 1

EXAMPLE 4 By using l00c.c. of benzene, 0.228 g. of titaniumbutoxytrichloride, 0.606g. of diethylaluminum chloride, 0.021g.-oftriphenyl phosphate, 0.064g. of dimethyl sulfoxide and 62g. of a BBfraction (having the same composition as in Example 2), the sametreatment as in Example 1 was carried out.

A cyclododecatriene fraction was obtained in an i amount of 15.2g.(99.89 percent pure) in a yield of 66.1 per cent. I

When a crude B- -Bfraction (having the same composition as in Example 1except thecyclopentadiene content was 0.15 percent) was used-as astarting material without treating it beforehand, 5.1g. ofcyclododecatriene fraction (8 1.10 percent pure) was obtained-in a yieldof 18 percent.

" EXAMPLE 5 When 62g. of a BB fraction (having the same composition asin Example 3) wasused under the same conditions as in Example 4, acyclododecatriene fraction (98.40 percent pure) was obtained in anamount of 14.2'g. and in a yield of 60.8 per cent.

EXAMPLE 6 I By using 100 c.c. of benzene, 0.340g. oftetrabutoxytitanium, 0.606 g. of diethylaluminum chloride,

j 0.021g. of triph'enyi phosphate, 0.064g. of dimethyl sulfoxide and62g. of a BB fraction (having the same composition as in Example 2), thesame treatment as in Example 1 was carried out. A cyclododecatrienefraction was obtained in an amount of 8.8g. (99.25 percent pure) in ayield of 38 per cent.

When 62g. ofa crude B-B fraction (having the same composition as inExample6 except the cyclopentadiene content was 0. l percent) was usedas a starting material without treating it beforehand, acyclododecatriene fraction was obtained in an amount of 0.89g. (80.5percent pure) in a yield of 3 per cent.

EXAMPLE 7 By using 100c.c. of toluene, 0.l90g. of tetrachlorotitanium,0.50 g. of diethylaluminum chloride, 0.02 g. of triphenyl phosphate,0.05 g. of dimethyl sulfoxide and 62g. of a B-B fraction (having thesame composition as in Example 2), the same treatment as in Example 1was carried out.

A cyclododecatriene fraction was obtained in an amount of 12.1 g. (98.9percent pure) in a yield of 52 percent.

EXAMPLE 8 By using l00c.c. of toluene, 0.256g. ofdibutoxydichlorotitanium, 0.98 g. of ethylaluminum sesquichloride, 0.02g. of triphenyl phosphate, 0.05g. of dimethyl sulfoxide and 62g. of a BBfraction (having the same composition as in Example 1), the sametreatment as in Example 1 was carried out.

A cyclododecatriene fraction was obtained in an amount of 13.0g. (98.7percent pure) in a yield of 56 per cent.

What is claimed is:

1. A process for producing cyclododecatriene-l,5,9 comprising contactinga 843 fraction (containing 25 90 weight percent of butadiene, of whichfraction the cyclopentadiene content is controlled to less than 0.1weight percent, with a Ziegler type catalyst comprising, in combination,(I) a titanium compound, (II) an aluminum compound, and (III) anelectron-donor compound containing phosphorus (IIIA) and anelectrondonor compound containing sulphur (IIIB), thereby causing thebutadiene to undergo cyclic trimerization.

2. A process for producing cyclododecatriene-l,5,9 as claimed in claim 1in which said B-B fraction is a distillation'product of crude B-Bfraction which has been derived from naphtha cracking and comprises:

by weight l,3-butadiene 25 to 50 butane butene 50 to 70 allene 0.02 to 2methylacetylene 0.02 to 2 ethylacetylene 0.05 to 2 vinylacetylene 0.05to 2 cyclopentadiene 0.1 to 2 3. A process for producingcyclododecatriene-l,5,9 as claimed in claim 1 in which said B-B fractioncontains 60 to percent by weight of butadiene.

4. A process for producing cyclododecatriene-l,5,9 as claimed in claim 1in which said titanium compound (I) has the general formula:

wherein X is halogen, Y is alkoxy, cycloalkoxy, or chloroalkoxy, eachalkoxy group having from one to 10 carbon atoms, acetylacetonato,aryloxy, or a chloroaryloxy, each aryloxy group being selected from thegroup consisting of phenoxy and methyl-substituted phenoxies, and-n is apositive integer of from 0 to 4, inclusive, and said aluminum compound(II) has the general formula:

wherein R is alkyl or cycloalkyl of one to 10 carbon atoms, arylselected from the group consisting of phenyl and methyl-substitutedphenyls, and m is 1.5 or 2, the mole ratio of the compound (ID/thecompound (I) being I to I00.

5. A process for producing cyclododecatriene-l,5,9 as claimed in claim 1in which said electron-donor compound containing phosphorus (IIIA) hasthe general formula:

POR'Q,

wherein R" is alkyl or cycloalkyl having from one to 10 carbon atoms,aryl selected from the-group consisting of phenyl and methyl substitutedphenyls, alkoxy of one to 10 carbon atoms, or aryloxy selected from thegroup consisting of phenoxy and methyl-substituted phenoxies, and saidelectron donor compound containing sulphur (IIIB) has the generalfonnula:

SORIIIz wherein R is alkyl having one to 10 carbon atoms, or arylselected from the group consisting of phenyl and methyl-substitutedphenyls, the mole ratio of the (compound IIIA compound IIIB)/thetitanium compound (I) being 0.01 to 4.0, and the mole ratio of thecompound IIIA/the compound lIIB being 0.01 to 10.0.

6. A process for producing cyclododecatriene-l,5 ,9 as claimed in claim1 in which said catalyst is produced by adding the aluminum compound(II) to a mixture of the titanium compound (I) and the electron-donorcompound IIIA and IIIB. I

7. A process forproducing cyclododecatriene-l,5,9 as claimed in claim 1in which said B-B fraction is caused to contact the Ziegler catalyst inan organicsolvent.

. t t t 0

2. A process for producing cyclododecatriene-1,5,9 as claimed in claim 1in which said B-B fraction is a distillation product of crude B-Bfraction which has been derived from naphtha cracking and comprises: %by weight 1,3-butadiene 25 to 50 butane + butene 50 to 70 allene 0.02 to2 methylacetylene 0.02 to 2 ethylacetylene 0.05 to 2 vinylacetylene 0.05to 2 cyclopentadiene 0.1 to 2
 3. A process for producingcyclododecatriene-1,5,9 as claimed in claim 1 in which said B-B fractioncontains 60 to 90 percent by weight of butadiene.
 4. A process forproducing cyclododecatriene-1,5,9 as claimed in claim 1 in which saidtitanium compound (I) has the general formula: TiXnY4 n wherein X ishalogen, Y is alkoxy, cycloalkoxy, or chloroalkoxy, each alkoxy grouphaving from one to 10 carbon atoms, acetylacetonato, aryloxy, or achloroaryloxy, each aryloxy group being selected from the groupconsisting of phenoxy and methyl-substituted phenoxies, and n is apositive integer of from 0 to 4, inclusive, and sAid aluminum compound(II) has the general formula: AlR''mCl3 m wherein R'' is alkyl orcycloalkyl of one to 10 carbon atoms, aryl selected from the groupconsisting of phenyl and methyl-substituted phenyls, and m is 1.5 or 2,the mole ratio of the compound (II)/the compound (I) being 1 to
 100. 5.A process for producing cyclododecatriene-1,5,9 as claimed in claim 1 inwhich said electron-donor compound containing phosphorus (IIIA) has thegeneral formula: POR''''3 wherein R'''' is alkyl or cycloalkyl havingfrom one to 10 carbon atoms, aryl selected from the group consisting ofphenyl and methyl substituted phenyls, alkoxy of one to 10 carbon atoms,or aryloxy selected from the group consisting of phenoxy andmethyl-substituted phenoxies, and said electron donor compoundcontaining sulphur (IIIB) has the general formula: SOR''''''2 whereinR'''''' is alkyl having one to 10 carbon atoms, or aryl selected fromthe group consisting of phenyl and methyl-substituted phenyls, the moleratio of the (compound IIIA -compound IIIB)/the titanium compound (I)being 0.01 to 4.0, and the mole ratio of the compound IIIA/the compoundIIIB being 0.01 to 10.0.
 6. A process for producingcyclododecatriene-1,5,9 as claimed in claim 1 in which said catalyst isproduced by adding the aluminum compound (II) to a mixture of thetitanium compound (I) and the electron-donor compound IIIA and IIIB. 7.A process for producing cyclododecatriene-1,5,9 as claimed in claim 1 inwhich said B-B fraction is caused to contact the Ziegler catalyst in anorganic solvent.